Succinic acid esters and hydraulic fluids therefrom

ABSTRACT

Hydraulic fluids contain as novel dispersants, reaction products of di- or trisuccinic anhydrides with polyethoxylated alcohols to produce polyethoxylated hydrocarbyl polyanhydrides.

This is a continuation of application Ser. No. 886,776 filed Jul. 17,1986 now U.S. Pat. No. 4,689,166.

FIELD OF THE INVENTION

This invention relates to new hydrocarbyl succinic esters and moreparticularly to aqueous based hydraulic fluids which contain hydrocarbylsuccinic acid esters, which hydraulic fluids have improvedcharacteristics in being stable and possessing excellent hard waterstability.

BACKGROUND

Aqueous based hydraulic fluids are well known in the art as exemplified,for example, by U.S. Pat. Nos. 3,580,847, 4,151,099, 3,657,123,3,005,776, 2,944,976, and 4,257,902. These aqueous based hydraulicfluids are used in various areas as mechanical power or pressuretransmitting media in situations where lubricating and wear preventingcharacteristics are necessary. In the technology of hydraulic powertransmission, mechanical power is imparted to a fluid called a hydraulicfluid in the form of pressure by means of a hydraulic pump. Power isutilized where desired by tapping a source of the hydraulic fluid andtransforming the power as pressure back to mechanical motion by ahydraulic motor. The hydraulic fluid is utilized as a pressure andvolume transmitting medium and any non-compressible fluid can performthe function. Water is the oldest fluid used for this purpose and isstill sometimes used without additives. In the prior art, however, therehas been heavy emphasis on the development of aqueous based fluids whichcontain various types of additives and which are designed andmanufactured specifically for specialty used.

Within any hydraulic system there are found such metals as iron, brass,solder, bronze, aluminum, zinc, cadmium and other commonly used metalsand the presence of several metals in a hydraulic system provides thepossibility for the formation of various corrosion problems. Therefore,such fluids traditionally contain corrosion inhibitors.

Such fluids also generally contain emulsifying agent or dispersants andvarious other additives such as thickening agents, freezing pointdepressants, antiwear agents, and various other additive designed tomeet problems encountered in use of the hydraulic or functional fluids.

It is also known that lubricating compositions including powertransmitting fluids can contain hydrocarbon substituted succinic acidesters wherein the hydrocarbon substituent is an aliphatic carbon chaincontaining a large number of carbon atoms. Such products are disclosed,for example, in U.S. Pat. No. 3,381,022 which describes oil solubleesters, diesters and mixtures of substantially saturated polymerizedolefin substituted succinic acid with mono or polyhydric aliphaticalcohols having up to 40 carbon atoms wherein the polymerized olefinsubstituent has at least about 50 aliphatic carbon atoms and a molecularweight of about 700 to 5000, with no more than 5% olefinic linkages.These succinic acid esters are described as being useful as additives inlubricants to impart detergent properties to the lubricant particularlyunder high and low temperature conditions. There is no disclosure,however, for incorporation of these lubricants into water basedhydraulic fluids.

U.S. Pat. No. 4,368,133 describes aqueous systems containing functionaladditives which contain solubilizers made by reacting an alkylsubstituted succinic anhydride containing about 12 to 500 carbon atomswith an alkanolamine. These compositions are water based hydraulicfluids and the succinic anhydride-alkanolamide reaction products arepresent as solubilizing agents.

U.S. Pat. No. 4,440,902 describes diesters of alkenyl succinic acids andethylene oxide/propylene oxide block polymers and their use asdemulsifiers for oil water emulsions and as corrosion protective agentsand dispersants for dyestuffs. Similarly, U.S. Pat. No. 3,957,854describes ester-containing compositions useful as additives in normallyliquid fuels and lubricants wherein the oil soluble carboxylic acidesters are prepared by reacting an aliphatic hydrocarbon polycarboxylicacid acylating agent containing at least 30 aliphatic carbon atoms withat least one polyalkylene glycol which is a demulsifier for an aqueousemulsion, and at least one primary or secondary amine.

U.S. Pat. No. 4,036,772 discloses esters formed from high molecularweight carboxylic acids derived from low molecular weight ethylenicallyunsaturated carboxylic acid reagents and oxidized ethylene propyleneinterpolymers with mono or polyhydric alcohols. These esters are said tobe useful in lubricant compositions and normally liquid fuelcompositions.

It is also known from U.S. Pat. No. 4,256,605 and related U.S. Pats.Nos. 4,504,275, 4,504,276, and 4,509,950 that compositions useful assurfactants in the emulsification of oils in aqueous media may beobtained by blending two types of polyesters which are the products ofcondensation of an alkenyl succinic anhydride with a polyalkyleneglycol. One type of polyester is derived from an anhydride in which thealkenyl group contains 40 to 500 carbon atoms, such as polyisobutenylsuccinic anhydride, and the other type is derived from an anhydride inwhich the alkenyl group contains 8 to 18 carbon atoms. Thesecompositions are said to be superior to the use of the polyesterseparately in providing emulsions of high stability produced with a lowenergy output. As acknowledged in column 1 of these patents, BritishPatent No. 1,055,337 discloses esters obtained by the reaction ofsaturated hydrocarbon substituted succinic anhydrides containing atleast 50 aliphatic carbon atoms in the substituent group with apolyhydric alcohol such as an alkylene glycol or polyalkylene glycol,and the use of such esters as additives for the purpose of impartingdetergent properties to lubricant. This British patent corresponds toU.S. Pat. No. 3,381,022, discussed herein.

U.S. Pats. Nos. 3,045,042, 3,255,108, 4,481,125, 4,447,348, 3,419,665,3,640,872, 2,993,773, 3,579,453, and 3,694,176 also disclose succinicacid esters wherein the ester moiety is a hydrocarbon or substitutedhydrocarbon, and use of such esters in aqueous based hydraulic fluids ofvarious types.

In none of this known prior art, however, are there to Applicant'sknowledge description of substituted succinic acid esters and resultingaqueous based hydraulic fluids which are particularly useful in havinghigh stability in hard water and in other areas where high water contenthydraulic fluids are used.

SUMMARY OF THE INVENTION

It is accordingly one object of the present invention to provide anaqueous based hydraulic fluid composition which is particularly suitablefor use in hard water based systems and provides excellent stability insuch systems.

A further object of the present invention is to provide a dispersantcomposition comprising the reaction product of an alkenyl succinicanydride and a polyethoxylated alcohol and use of such dispersantcompositions in aqueous based hydraulic fluids.

An even further object of the present invention is to provide novelesters which are made by the reaction of a hydrocarbyl succinicanhydride wherein the hydrocarbyl substituent contains unsaturation,with an excess of a polyethoxylated alcohol under such conditions that ahigh percentage of the anhydride reactant is converted to thecorresponding diester, and the use of such reaction products as surfaceactive agents or dispersants to stabilize high water content hydraulicfluids, particularly, when used in water of significant hardness.

Other objects and advantages of the present invention will becomeapparent as the description thereof proceeds.

In satisfaction of the foregoing objects and advantages, there isprovided by the present invention ethoxylated esters of succinicanhydride which are useful as dispersants and more particularly, esterreaction products of long chain hydrocarbyl substituted succinicanhydride with polyethoxylated alcohols and use of these compositions asdispersants or surface active agents.

The present invention also provides an aqueous based hydraulic fluidhaving characteristics making it particularly suitable for use in waterof significant hardness, which composition comprises a dispersant whichis an ester reaction product of a hydrocarbyl substituted succinicanhydride with an excess of a polyethoxylated alcohol, a surfactant,corrosion inhibitors and water.

Also provided by the present invention are methods for preparation ofthe novel dispersant and hydraulic fluid and methods for use of theaqueous based hydraulic fluid of this invention.

DESCRIPTION OF PREFERRED EMBODIMENTS

The present invention relates to a novel group of succinic acid esterswhich are useful as dispersants in a series of aqueous based hydraulicfluids. The succinic acid esters are produced in general by a series ofreactions starting with the reaction of a hydrocarbyl substitutedsuccinic anhydride with at least one equivalent, preferably 1-3equivalents, of maleic anhydride to produce a succinic anhydride of thefollowing formula: ##STR1##

In the above formula, R is a hydrocarbyl or hydrocarbon substituentwhich contains at least about 10 carbon atoms. Preferably R containsolefinic unsaturation and branch chained configurations and provides thestarting succinic anhydride with a molecular weight in the range ofabout about 700.

The reaction between the hydrocarbon substituted succinic anhydride andthe maleic anhydride to produce the compound of Formula (I) is conductedby heating the succinic anhydride reactant to a temperature of about150°-200° C. and thereafter adding at least one equivalent of the maleicanhydride to the succinic anhydride over a period of time such as 1 to 3hours. After the addition is complete, the reaction mixture is thenagitated for 2 to 4 hours to complete the reaction.

In an alternative procedure, the reaction product of succinic anhydrideand one equivalent of maleic anhydride may then be further reacted withadditional equivalents of maleic anhydride to add the additionalanhydride groups so that the intermediate product may contain 3 or 4anhydride groups. However, for purposes of use as a dispersant afterrection with alcohol, the basic product containing two anhydride groupsperforms satisfactorily.

The initial starting material, hydrocarbylsubstituted succinic acid iswell known in the art and is disclosed for example in U.S. Pats. Nos.3,923,669, 3,428,561, 4,086,251, and 4,450,281, the disclosures of whichare incorporated herein by reference. As described in those patents andherein, the hydrocarbyl group R may be defined as a hydrocarbon whichcontains at least 10 carbon atoms. Preferably the hydrocarbyl groupcontains olefinic unsaturation but is otherwise substantially saturatedor contains an armoatic ring. The olefinic unsaturation may beconjugated or nonconjugated and may be derived from diolefins, olefinicpetroleum fractions and polyunsaturated polymers, oligomers, andcopolymers. The polyunsaturated polymers are usually those derived bycopolymerization of lower monoolefins with lower diolefins. Both typesof olefins contain up to 12 carbon atoms. Suitable monoolefins includeethylene, propylene, 1-butene, 2-butene, isobutene and the pentenes,hexenes, and heptenes (all isomers included). Suitable diolefins includebutadiene, 1,5-hexadiene, norbornadiene 1,5-dodecadiene, and the like.Furthermore, the olefin polymer can contain alicyclic or aromatic groupswhich may be derived from such monomers as cyclopentene, cyclohexene,1,4-cyclohexadiene methylene cyclopentene, methylene cyclohexene,α-pinene, styrene, vinyl toluene, α-methylstyrene, and3-phenyl-1,5-hexadiene. The preferred R group will provide a molecularweight to the starting material of about 700-3000. A preferred R is analkyl or alkenyl group having a molecular weight of at least 800.Polyalkenyl succinic anhydride represents a preferred general class ofstarting materials. Polyisobutenyl succinic anhydride is especiallypreferred. This material has a molecular weight of about 1000 to 1400and is available commercially from Humphrey Chemical Company and Texaco.

The resulting dianhydride product of Formula (I) is then reacted with amolar excess of a polyethoxylated alcohol of the formula R'(OCH₂CH₂)_(x) OH, wherein R' is an alkyl, alkenyl, aralkyl or alkaryl groupcontaining 1 to about 20 carbon atoms to produce the product of theinvention. In conducting this reaction it is preferred to use about 3 to6 moles, preferably 3 moles, of polyethoxylated alcohol per mole ofhydrocarbyl succinic acid anhydride, but a larger excess may be used.The resulting product consists primarily of the esterified succinic acidof the following formula: ##STR2## wherein R and R' are as describedabove, x is an integer of about 6 to 10 and n is 0, 1 or 2.

The reaction conditions for producing the polyester of Formula (II) aresuch that a very high percentage of the anhydride is converted to thediester derivative. However, a small amount of intermediate reactionproducts are present such as the product wherein some of the groups areesterified and others remain in the acid form. Also, since an excess ofthe alcohol is used, some free unreacted alcohol will also usually bepresent. It is an advantage of the present invention that a small amountof the partially esterified product and starting alcohol be present incombination with the fully esterified product since better performanceis achieved in obtaining maximum stability when used in high watercontent fluids wherein the water is of significant hardness. Therefore,the present invention is inclusive of use of the completely esterifiedproduct of Formula (II) as the dispersant in hydraulic fluids, as wellas mixtures in any proportions of the completely esterified product withpartially esterified products of the following formula. Such productsmay be defined by the following formula, the products also beinginclusive of mixtures with the alcohol: ##STR3## wherein n is 0, 1 or 2,R' is alkyl, alkenyl, aralkyl, or an alkaryl group containing 1 to about20 carbon atoms and y is zero or an integer of 6 to 10, provided that atleast one y but no more than 3 is zero, and when y is zero, R' ishydrogen, and also including proportions of unreated alcohol in amountsof up to about 25% by weight.

The esterification reaction to produce the product of Formula (II) isconducted by heating the succinic anhydride intermediate of Formula (I)with a catalytic amount of an acid catalyst such as an alkali metal ofacetic acid, as well as acid catalysts which are typically used totransform anhydrides and acids to esters, such as p-toluene sulfonicacid. Lithium acetate is particularly satisfactory. Sodium acetate andpotassium acetate may also be used. These catalysts are used incatalytic amounts about 0.01 to 1.0 wt. %. The appropriatepolyethoxylated alcohol or corresponding phenol or mixture thereof isthen added to the heated succinic anhydride which should be at atemperature of about 100°-150° C. At least about three equivalents, andpreferably three to six, most preferably three equivalents, of thepolyethoxylated alcohol should be used per equivalent of succinicanhydride reactant. After addition of the polyethoxylated alcohol, thereaction mixture should then be stirred for about 2 to 10 hours untilthe total acid number of the reaction mixture is below 10. The totalacid number is obtained by titration of a sample of the product withpotassium hydroxide so that the value of 10 means 10 milligrams of KOHper gram of compound.

After preparation of the esterified product defined above by Formula(II), the resulting compound or mixture of compounds of Formula (III)may be used as the dispersant component in the formulation of an aqueousbased hydraulic fluid. The esterified product of Formula (II) may beused without purification since it is desirable that a small amount ofthe intermediate reaction products (Formula III), such as half or onequarter esters and some alcohol starting material, have been found tocontribute to performance of the ester for stability of the hydraulicfluid. Thus, the preferred composition of this invention will containthe completely esterified product as well as partial esters and somealcoholic starting material.

This ester product of mixture is used as the dispersant in formulationof an aqueous based hydraulic fluid which will also typically containoil, an anti wear additive and corrosion inhibitors. Particularformulations of hydraulic fluid comprise the following:

    ______________________________________                                        Component           Amounts                                                   ______________________________________                                        Dispersant (Formula II or III)                                                                    10-40 wt. %                                               Surfactant          15-30 wt. %                                               Corrosion inhibitors                                                                               5-30 wt. %                                               Water               Balance                                                   ______________________________________                                    

In the above formulation, the dispersant, which is preferably present inan amount of about 12-16%, will be the inventive composition defined byFormula (II) mixtures of this composition with partially esterifiedproducts and starting alcohol as defined in Formula (III). Thesurfactant which is preferably present in amounts of about 18-22%, ismost preferably a polyethoxylated octylphenol product which is availablefrom the Rohm & Haas Company under the tradename "Triton" andparticularly "Triton X-100". Preferred corrosion inhibitors includecopper corrosion inhibitors as well as amines. The copper corrosioninhibitors are preferably present in amounts of about 7 to 10% and areparticularly suitable when the hydraulic fluid is used with bearingswhich contain copper alloys. Satisfactory copper corrosion inhibitorsinclude sodium mercaptobenzothiozoles, available from the R. T.Vanderbilt Corporation under the tradename "NACAP". Particularlypreferred amines which are useful as vapor phase corrosion inhibitors,that is which inhibit corrosion just above the surface of the fluidinclude diethanolamine, monoethanolamine, dimethylethanolamine and thelike.

The composition may also contain anti-wear additives such as zincdialkyldithiophosphate, sold by The Lubrizol Corporation for thispurpose, phosphate esters, or other known anti-wear agents. Anti-foamagents such as Foam Ban MS-30 sold by Ultra Adhesive Corporation, mayalso be included, as well as various other known additives for suchhydraulic fluids, depending on the ultimate use. Anti-wear agents,antifoam agents and the like are present in amounts of about 0.1 to 10%by weight. Anti-wear agents are preferably present in an amount of about0.6 wt. %. The remainder of the composition will comprise water which ispresent in amounts which are not considered critical, but which mayrange from 20 to 80% by weight.

Aqueous based hydraulic fluids produced from the above formulation andusing esters made from di- and trianhydrides of the invention are stablein water of extreme hardness for 7 days or more while maintained at 70°C. Water of extreme hardness is defined as containing at least 1500 ppmof calcium carbonate. On the other hand, hydraulic fluids produced byesterification of the monoanhydride were found to be stable in water ofonly 1000 ppm of calcium carbonate hardness for 7 days at 70° C. Thus,the ethoxylated esters of the present invention have outstandingadvantages as dispersants, particularly when used in water of highmineral content, which makes the compositions particularly useful incertain areas.

The following examples are present to illustrate the invention but it isnot to be considered as limited thereto. In the examples and throughoutthe specification, parts are by weight unless otherwise indicated.

EXAMPLE 1

In this example polyalkenyl succinic anhydride is heated to 170° C. and1 molar equivalent of maleic anhydride is added slowly to the succinicanhydride over a period of 2 hours. After the addition is complete, thereaction mixture is then stirred for 3 hours without additionalprocessing. This reaction produces the polyalkenyl disuccinic anhydride.

EXAMPLE 2

The polyalkenyl succinic anhydride starting material used in Example 1is heated to 170° C. and 2 equivalents of maleic anhydride are addedslowly over a period of 3 hours. After the addition is complete, thereaction mixture is stirred for 12 hours. This produces the polyalkenyltrisuccinic anydride or the derivative which contains three anhydridegroups.

EXAMPLE 3

Polyalkenyl succinic anhydride containing a single anhydride group isheated to 120° C. in combination with a catalytic amount of lithiumacetate. Thereafter, a polyethoxylated alcohol is added in an amount of3 equivalents of alcohol per equivalent of succinic anhydride. Afteraddition of the alcohol, the reaction mixture is stirred for 5 hoursuntil the total acid number is reduced to below 10 milligrams of KOH pergram of compound, which is obtained by titration with potassiumhydroxide.

EXAMPLE 4

In this example the dianhydride produced from Example 1 is heated to120° C. in combination with a catalytic amount of lithium acetate.Thereafter 3 equivalents per anhydride of polyethoxylated alcohol isadded to the reaction mixture and stirring is continued for 5 hoursuntil the total acid number is reduced to below 10 milligrams of KOH pergram of compound.

EXAMPLE 5

Polyalkenyl trisuccinic anhydride produced in Example 2 was heated to120° C. in combination with a catalytic amount of lithium acetate.Thereafter, 3 equivalents per anhydride of a polyethoxylated alcohol isadded to the mixture and stirred for 5 hours until the total acid numberwas reduced to below 10 milligrams of KOH per gram of compound.

EXAMPLE 6

The dispersants described as being produced in Examples 3, 4 and 5 werethen formulated as aqueous based hydraulic fluids. The aqueous basedhydraulic fluid contained the following formulation wherein thedispersant is the reaction product of Examples 3, 4 or 5:

    ______________________________________                                        Component            Amounts                                                  ______________________________________                                        Dispersant (Formulation A, B, C)                                                                   14        wt. %                                          Surfactant           20        wt. %                                          Copper corrosion inhibitors                                                                        8.6       wt. %                                          Amine                20.4      wt. %                                          Water                37%                                                      ______________________________________                                    

In the above formulation, the dispersant in Formulation A is theesterified monoanhydride of Example 3; the second formulation is theesterified dianhydride of Example 4, and the third formulation is theesterified trianhydride of Example 5. The surfactant in all cases wasTriton X-100, which is a polyethoxylated octylphenol. The coppercorrosion inhibitor is NACAP, which is sold by the R. T. VanderbiltCorporation as a tradename for sodium mercaptobenzothiozole. The amines,which are vapor phase corrosion inhibitors, are diethanolamine andmonoethanolamine.

The aqueous based hydraulic fluids made from the esters of the di andtrianhydrides were found to be stable in water of extreme hardness, thatis, up to 1500 ppm of calcium carbonate for more than 7 days whileoperating at 70° C. However, those made from the monoanhydride werefound to be stable in water of only up to 1000 ppm calcium carbonatehardness for 7 days at 70° C.

The invention has been described herein with reference to certainpreferred embodiments. However, as obvious variations thereon willbecome apparent to those skilled in the art, the invention is not to beconsidered as limited thereto.

What is claimed is:
 1. An aqueous based hydraulic fluid comprising thefollowing formulation:

    ______________________________________                                        Component            Amounts                                                  ______________________________________                                        Dispersant           10-40 wt. %                                              Surfactant           15-30 wt. %                                              Corrosion inhibitors  5-30 wt. %                                              Water                Balance                                                  ______________________________________                                    

wherein the dispersant comprises a water dispersible polyethoxylatedester of the following formula: ##STR4## wherein x is an integer rangingfrom about 6 to 10, R is a hydrocarbyl group which contains at leastabout 10 carbon atoms, and R' is an alkyl, alkenyl, aralkyl, or alkarylgroup which contains from 1 to 20 carbon atoms.
 2. An aqueous basedhydraulic fluid according to claim 1, wherein R is an alkyl or alkenylgroup having a molecular weight of at least
 800. 3. An aqueous basedhydraulic fluid according to claim 1, wherein R' is alkyl or alkaryl. 4.An aqueous based hydraulic fluid according to claim 1, wherein R isalkyl or alkenyl having a molecular weight of at least 800 and R' isalkyl or aralkyl of 10 to 20 carbon atoms.
 5. An aqueous based hydraulicfluid according to claim 1, wherein R is polyalkenyl.
 6. An aqueousbased hydraulic fluid according to claim 1, wherein R is a hydrocarbylgroup having a molecular weight of about 600 to
 2900. 7. An aqueousbased hydraulic fluid comprising the following formulation:

    ______________________________________                                        Component            Amounts                                                  ______________________________________                                        Dispersant           10-40 wt. %                                              Surfactant           15-30 wt. %                                              Corrosion inhibitors  5-30 wt. %                                              Water                Balance                                                  ______________________________________                                    

wherein the dispersant comprises a mixture comprising a waterdispersible polyethoxylated ester of the formula: ##STR5## a waterdispersible partially esterified ester of the formula ##STR6## and apolyethoxylated alcohol of the formula

    R'(OCH.sub.2 CH.sub.2).sub.x OH

wherein x is an integer of from 6 to 10, R is a hydrocarbyl groupcontaining at least 10 carbon atoms, and R' is alkyl, alkenyl, aralkylor an alkaryl group having 1 to 20 carbon atoms.
 8. An aqueous basedhydraulic fluid as in claim 1 which also contains an anti-wear agent. 9.An aqueous based hydraulic fluid as in claim 7 which also contains ananti-wear agent.
 10. An aqueous based hydraulic fluid according to claim7 wherein R is a hydrocarbyl group having a molecular weight of about600 to 2900.